Igniting composition



Patented Nov. 12, 1946 ENT OFFICE IGNITING, COMPOSITION Ludwig Audrieth,Dover, N. J.

No Drawing. Application March 13, 1945, Serial No. 582,478

(Granted undenthe act of March 3, 1883, as

4 Claims.

The invention described herein may be manufactured and used by or forthe Government for governmental purposes, without the payment to me ofany royalty thereon.

This invention deals with new and improved igniting compositions whichare characterized (a) by the fact that they contain polymericthiocyanogen and (b) by the superior functioning characteristics of suchmixtures due to the incorporation-of polymeric thiocyanogen which servesas a more efiicient fuel and reducing agent and in certain instances asa sensitizer.

While igniting compositions are being used for a wide variety ofpurposes, such as for example in'primers, delay elements, fuzes and thelike, it is significant that all of them consist essentially of anoxidizing agent or oxygen rich material in combination with a reducingagent or fuel.

oxidizing agents which are used include, for example, such materials asthe alkali and alkaline earth perchlorates, chlorates, chlorites,nitrates, oxides, peroxides, chromates, permanganates, brornates,iodates and periodates. Fuels and reducingagents maybe chosen from amongthe following types of chemical substances: (a) metals, such asmagnesium, aluminum, boron, silicon, zirconium, (b) non-metals such assulfur, selenium, tellurium, carbon, alloys such as magnesium-aluminum,calcium-silicon and (d) compounds such as lead and copper thiocyanate,metallic sulfides, selenides and tellurides. Other agents are also addedto the oxidizing agent-fuel combination to achieve specific effects forparticular uses and purposes. Thus, sensitizer-s and high explosives areadded to priming compositions in order to increase both friction andstab sensitivity, as well as flame volume. Binders consisting of naturalor synthetic resins, waxes, and phaltum are often added to delay andigniter compositions to make such mixtures more readily pelletable andmore easily ignitable. However, in spite of the aforementioned modifyingagents it is still the oxidizing agent fuel combination which serves asthe basis for these compositions of matter.

The particular combination of oxidizing agent plus fuel determineslargely whether the mixture under consideration will be (a) friction orstab sensitive in which event such a product will serve as a primer,(1)) will ignite readily with the evolution of considerable heat whichcharacteristics amended April 30, 1928; 370 O. G. 757) trains of fuzesor as the delay components of fuzes. From a practical point of View manyother factors must also beconsidered in the developmentof suchcompositions as for example: (a) stability on magazine storage and alsoat the high and low temperatures and the extremely dry and very humidconditions met with under present conditions of warfare; (b) ease ofblending of the ingredients to insure homogeneity and uniformity inchemical composition; and (0) safety in the manufacture, loading andhandling of these mixtures.

I have found that polymeric thiocyanogen is an exceptionally eflicientfuel in combination with a wide variety of oxidizing agents yieldingprimer, delay, fuze and igniter compositions which possess markedadvantages over materials now used in the military arts; both withrespect to stability and functioning characteristics. Insofar as can bediscerned from atho-rougli examination of the pertinent literature andof the priorart no compositionscontaining polymeric thiocyanogen haveever been suggested or used for the purpose outlined lierein.

Lest there be some confusion concerning polymeric thiocyanogen and itsproperties, I shall present herewith a, short description of this newandsuperior ingredient of primer, delay, fuze and igniter' compositions.Polymeric thiocyanogen is also designated in the literature aspolythiocyan ogen and as parathiocyanogen and is represented by theformula (SCNM. Actually its composition does not conform exactly withthis empirical formula since it contains chemically combined both o ygenand hydrogen with the result that an elementary analysis gives valuesvarying from 45-55% sulfur. It is significant, however, thatirrespective of the mode of preparation, all products' produceessentially similar X-ray diffraction patterns demonstratingthat suchmaterials while not identical with respect to exact chemical compositionnevertheless do possess the same molecular structure. It thus makeslittle diiference whether polymeric thiocyanogen is prepared (a) byanodicoxiclation or (b) by chemical interaction of oxidizing agents suchas hydrogen peroxide, the halogens and the like with thiocyanic acidand/or thiocyanates, in aqueous or non- In presenting the examples'givenherein I do not wish to limit myself to the exact proportions of thevarious ingredients nor to the particular oxidizing agent cited forpurposes of illustration. Thi is especially true in the case of delayand fuze powders where changes in proportions will make it possible tochange the burning times to adapt such compositions for use in aparticular component. That changes in the ratios of polymericthiocyanogen to other ingredients makes it possible to vary the burningtime may be looked upon as one of the advantages to be derived in thepractical use of such mixtures. In all of the examples noted hereinmanufacture of the com- Example I As examples where polymericthiocyanogen is employed, in non-fulminate containing primer mixtures,there may be cited the following compositions:

I II

Potassium chlorate; 51 64 Antimony sulfide 21 Polythiocyanogen Leadazide 5 Both compositions function with the rapid and even ignition ofthe entire charge and with the production of a hot flame which willinsure transmittal to the remainder of the explosive train. CompositionI is somewhat oxygen deficient in that a ratio of 60:40 parts ofpotassium chlorate to antimony sulfide is employed. In this instancepolymeric thiocyanogen serves both as an auxiliary fuel as well' as asensitizer, for without this agent much greater force is needed toeffect functioning of the mixture. Composition II contains sufficientchlorate to take care of the oxygen demand of both the antimony sulfideand the polymeric thiocyanogen. These examples are given inorder toindicate that the proportions of .the oxidizing agent to fuel may bevaried appreciably without affecting the functioning characteristics ofsuch mixtures. It is also pertinent in this connection to refer to theadvantage of polymeric thiocyanogen over metallic thiocyanates, such aslead thiocyanate, which are widely used as constituents of primingcompositions.

Whereas only approximately ten percent by weight of polymericthiocyanogen is required to obtain maximum effectiveness and sensitivityto stab action of compositions such as those given above, twenty totwenty-five percent of lead thiocyanate is required in order to evenapproach the very superior results obtained by incorporation of my newand improved fuel and reducing agent. It is furthermore significant thatpolymeric thiocyanogen is superior to sulfur as a sensitizer since it isnon-volatile and insoluble.

Example II 4 solvents, serving under these conditions as a primermixture for chemical fuzes.

Example III Fuze powders used in time trains are commonly modificationsof black powder consisting of potassium nitrate, carbon and sulfur inthe proportions 75:10:15. The manufacture of such-powders must becarefully controlled and incorporation of the ingredients to insurehomogeneity must be effected so that the proper burning time can beobtained. It is obvious that such homogeneity is much more readilyobtainable when only two ingredients are to be mixed. Thus a mixture ofpotassium nitrate and polymeric thiocyanogen, in equal parts by weight,produces a slow burning fuze powder which is all the more exceptional inthat it burns progressively yet uniformly, even if at a slow rate, andis also readily and easily ignitable. Replacement of the non-volatilepolymeric thiocyanogen for sulfur is another advantage of thiscomposition over black powder.

Polymeric thiocyanogen contains the necessary carbon and sulfur inchemical combination and, as pointed out under Example I, isnon-volatile and in this respect preferable over the sulfur ordinarilyemployed in black powder compositions. The addition of potassiumperchlorate or other oxidizing agent in percentages up to ten percentwill markedly speed up the burning time if a faster powder is desired.

Example IV Thecombination of barium peroxide and polymeric thiocyanogenin proportions of 95 to 5 or to 10 gives mixtures which are easilyignitable, evolve little gas and undergo reaction at an extremely rapidrate with the evolution of considerable heat. For the purposes ofprepelleting in order to facilitate loading operations in tracercomponents the addition of 1 to 2% of some binder, such as asphaltum,wax, natural or synthetic resins is desirable although not necessary.Such mixtures serve admirably as igniter compositions for tracercomponents. Increase in the percentage of polymeric thiocyanogen givescompositions which burn more slowly and may therefore serve as delaycompositions.

I have cited above typical cases to indicate that polymeric thiocyanogenin combination with various oxidizing agents will give mixtures whichwill serve a variety of useful purposes. I do not wish to be limited inthe scope of my invention to the specific examples given herein since itis indicated by laboratory tests that compositions containing polymericthiocyanogen in combination with a wide variety of oxidizing agents willfunction quite as satisfactorily as those described above.

I claim:

1. An igniting composition consisting essentially of polymericthiocyanogen and an oxidizing agent.

2. An igniting composition comprising potassium chlorate, polymericthiocyanogen, antimony sulfide and lead azide.

3. An igniting composition consisting essentially of potassium nitrateand polymeric thiocyanogen.

4. An igniting composition consisting essen tially of polymericthiocyanogen and barium peroxide.

LUDWIG F. AUDRIETH.

